Development of a solid oxide fuel cell anode by impregnating catalytic Ni and Ni-CeO2 nano-particles on 8YSZ fiber structure was carried out in this work. The nano-scale 8YSZ fibers were successfully fabricated by the electrospinning process and were well matched with the 8YSZ electrolyte. The experimental results demonstrated that the Ni/8YSZ anode with nano-8YSZ fibers, which impregnated with 3M nickel nitrate, decreases the polarization resistance and increases the exchange current density. However, the lowest polarization resistance and the highest exchange current density are observed in Ni/8YSZ fibers anode by adding nano-ceria particle from 5 wt.% to 10 wt.%. It is attributed to that the grain growth of Ni particle has been constrained by modifying appropriate amount of ceria particle to reduce the obstruction of diffusion path of fuel gas and to enhance the amount of triple phase boundary (TPB). On the other hand, 8YSZ nano-fibers provide a stabilized porous structure of the anode. Accordingly, nano-CeO2 particle provides storing and releasing of oxygen ion to improve the catalytic performance of nano-Ni modified 8YSZ fiber anode